Process for recovering by-products from plant substances and the like



Feb. 23 1926. y

F. K. FISH, JR

PROCESS FOR' RECOVERING BY- PRODUCTS FROM PLART sUs'rANGEs AND THE LIKE Filed Jan. 2. 1920 Patented F eb. 23, 1926.

UNIED STATS FREDERICK K. FISI-I, JR., 0Fv NEW YORK, N. Y.

PROCESS FORBECOVERING :BY-PRODUCTS FROM PLANT SUBSTANGES'AD THE LIKE.

Application tiled January 2, 1920, Serial No. 348,725.

improvements in a Process for Recovering By-Products from Plant Substances and the like, ot' which the following is a specication.

This invention relates to improvements in a process for recovering ley-products from plant substances and the like, such tor instance terpenes, turpentines, resins, gums, acids, alcohols, resinous matter, and other extractivas and the like.

Primarily the invention aims to utilize the terpenes, oils, acids, volatile components and other solvents combined with steam `or superheated water; at or about atmospheric pressure, or under higher pressure and to subsequently treat the substance, such, for example, as resinous bearing woods, in superheatcd water holding such extractors at a temperature above its normal boiling point, alternated with a vacuum, all of which will economically and quickly collect in one concentrated solution the various by-products of the substance, the solution thereafter being distilled or other wise treated to separate the different byproducts one. from the other, and ronfiftlfie` water in which the wood is treated In carrying out the invention as applied.

to plant substance as wood or woody libre l make use ot the fact that turpentines, oils and acidsof wood are eective solvents of the resins, gums or the like, or substances in the wood, and that all components of the oils of the wood, both those lighter than water and those heavier than Water are substantially soluble in one. another, l also make use .ot the fact that a vacuum lowers the boiling point of the constituents of the wood, and employ this expedient in .assisting in the accomplishment ot the de-l sired result.

@ne way of carrying out my improved- Witha door or doors,`an interior track 2,

l i i and spray pipe 2 controlledn by a valve 2X. rlhis chambermay be supplied with steam or superheated steam `through a pipe 3- controlled by a -valve 3", leading to a suitable source, or heat, such as steam or hot air and vapor may be introduced to the chamber through a pipe 19, leading toa container hereinafter referred to, and if desired heat such as steam or hot air may be introduced to .the chamber through coils, not shown.

' Communicating with the top of the sweat chamber is a pipe l which leads into an air tight hot box l, suitably heated by coils (not shown). Communicating 4with the oposite end of the hot bok is a pipe 1d, which eads into the bottom of the sweat box, a valve or valves l.e being provided to control the pipes. ln the pipel is a fan lf, to draw the vapors from the top of the sweat chamber, and pass them through the hot boxand' through the pipe 1d, and into the bottom of the sweat chamber. The an creates a suction throu h the sweat chamber, and quickly draws o the vapors and the latter are superheated in the hot box, and employed to act on the wood in the sweating step, The vapors are of course charged `with the terpenes, oils, gums, and the like,

which when superheated act to further the extraction of like constituents in the Wood. From the top or dome of the sweat-chamber extends a pipe 5, connected with coil 6 in a condenser 7, the coil extending into a collector tank l()o y A vacuum pump 9, connects at its suction cndthrough pipell'to a second coil 8 of condenser 7, discharging into collector tank l0. Coil 8 is connected at its upper end to a pipe 8a which leads to a container 13. l2 is a valved pipe'which connects the bottom of the sweat-chamber 1 and the collector tank 10, to carry oil the condensate from the lchamber to the tank., The condenser 7 may be cooled by any Well known coolin agent, as water or brine, which is circulate from a bottom inlet to an upper outlet, and is of the usual construction.

Located adjacent to and spaced from the sweat chamber 1,-is a container 13,.in which is a perforated coil '14, provided with a valve 14C, to supply steam to the interior of the container, and in\the latter also are steam heating coils 15 having valves l5 15. The container is also provided with a y door or doors, and in thecontainer there is a track 13x preferably in line with the track in the sweat chamber 1, and between the container 13 and the sweat chamber'v there will be a track for conveniently transferring apcar carrying a load of wood or `material from the sweat chamber 1 to the container 13 to be further treated. The pipe 8 connects with the top of the container, and in it is a safety-valve 18 which also may act as an ordinary controlling valve. The pipe 19, leading from the lower sweat-chamber '1 is connecte to a pipe 19, the ends of whic are conected vto the top of a tank 20, and thecontainer 13, the pipe 19 having controlling valves 19 and 19d fora ose ito be explained. f j

In the tank 20, are heating coils 24, hav'- ing valve 25, and condensation pipe 26, having a valve 25* connected with a steam trap 27, whichl preferably discharges through pi 28, tinto sweat-chamberl 1. e suction end of aforce-pump 29, is connected with the collection tank 10, by pipe 30, and tire dischar eend of said pump is connected tothe ta 20, by a pipe 31, having valve( 32.

An air compressor 33, is connected with container 13, y pipe 34, provided with a valve 35, and said pipe is connected with tank 20, by ja branch pipe 36, provided with a valve 37, .'Spitay pipe 38, connected with a sup ly ofcold" water yis installed at the top o container Vv13 `va ipev 39 provided with a valve 40, connects e container 13, with the collector .tankI 10. I

To effect'` th complete' removal of the more insoluble and heavier gums, .resinous,

or tar like constituents in some Wood, a chemical solution'may be employed. This solution 1s retained in a tank 50, and may be alkaline or acid or containlspecial ingredi- Nents whichwill act as an agent to dissolve end remove the resinous and like matter. in and from the wood. The tank may be connected to the container-13, by -a pipe 51,A

havin `a valve 52. A branch pipe 53, connects t e top-.of tank 5 0, with the compressed vair 'line `pipe 34, af valve 55 being em- .,ty V11 ployed to control the air passing through the pipe a'gcin the top of the tank is a safe'- ve f- In the tank ,50, ref'heatng coils 58, and steam coils 59.. .f

4In connection'lwitliithisstep it is' highly- `desirable thatfthe woodbe washed to Vre- 'cover any 'solution or resinous matter remainingv in 'fthe,wood, after the chemical solution' 'is withdrawn. Therefore I provide a reservoir-60,.` containing "cold water, and. connected to container 13, by a pipe 61v havin a valve 62. .To the reservoir is connecte a pipe 63 leading to a pressure apparatus (notshown) by means of which the water isfforced into the container, and this ortion of the yof collector-tank 10, are pumped into tank 20, and through the medium of heating coils 24, the .liquid is super-heated or in other words the temperature of the liquid is raised above its boiling point, and the pressure is consequently raised above atmosphere, to prepare it for quickly acting on p V later on when introduced into container 13.

Wood in any suitable form is loaded on a truck and run into the sweat-chamber 1, and live steam, super-heated steam, heated air or any combination of them are introduced through the pipe 3, and after the first truck load has passed through the sweat-chamber, and is under treatment in container 13, the steam from the container 13, is also utilized, as this is heavily charged with the turpentines removed from the wood while being in' the container.

Valves in the pipes 19 and 19a are regulated to allow the passage of steam as desired from either or both the container 13 and.Y

tank 20, into the sweat-chamber, land if necessary the vheat in the sweat-chamber may be augmented by heatjfromsuitable coils (not'shown).

It is desirabley hat the temperature of the wood in the ,sweat-chamber be raised above the joint. boiling point of turpentines and admi'xed liquid, usually water, and that the treatment ofthe wood during this step of the process be for one or two hours, depending upon the thickness and character of the wood or material being treated.

y The steam, and terpen'e or' like va ors in the sweat-chamber, penetrate and so n the entire structure of the wood, as well as the soluble gums and resins. At this temperature, the combination of steam and vapors reach even tov the interior of the separate .pieces and dissolve certain `are insoluble in water.

constituents which The wood. is thus prepared for a more ready and effective'v treatment in the container 13. The high heat reached in the sweat-chamber causes the constituentswhich have been softened to move to' a certain extent, -to the surface of thei `wood,',where they accumulate, producing'I in effect sweat, This surfacewise movement may be increased by the oc- `casional applicationl of 'cold 'water through spray pipe' 2,, the` sudden cooling of the surface of the wood or other material causing a partialcondensation of the vapors with a lessened pressure which causes a movement of the interior vapors, liquidsv contained therein, surfacewise.

IThe 'sweat-chamber being tightly closed some slight pressure therein will be created, and to relieve this pressure the vapors which have not been'previo'usly condensed pass through pipe 5, and are condensed in the'coil 6, and thereupon pass into collectortank 10 and may thereafter be pumped into the tank 20, to be used with the water inv subsequent treatment of the-wood. A portion ot the vapors are condensed in the sweat-chamber 1, and pass through the pipe 12. to the collector receptacle 10, for re-use in the process.

The condensate accumulated in the collector tank l0 will be pumped from time to time into tank 20 to add to the strength of 4the solvent liquor, and when the content `ol? the tank 20 becomes as concentrated as fmaydbe desired, it is drawn 0H and is separate f ln some instances it is preferable to super- Therefore, the valve 1 is opened and the tan lE sucks the liberated vapors from the top oi the sweat-chamber, and introduces vapors into the sealed hot box 16, .where they become heated, and are subsequently directed through the pipe 1d. The result of this action is to create a suction through the sweatchamber, which causes the vapors charged with the terpenes, oils, and other volatile substances introduced through pipe 1l to cooperatewith the steam and the vapors liberated from the wood, to co-mingle or mix and act promptly to dissolve and liberate other similar constitutents in the lwood. ln other'word's the charged vapor is, by this action employed as a solvent to act on the constituents in the Wood containing the byproducts to be recovered. While this action is going on a portion of the excess vapors are escaping'through the pipe 5, to the collector tank, and the condensate at the bottom of the chamber likewise passes to said tank.

After the wood has been treated in the sweat-chamber for a suihcient time to 'raise the temperature to the required degree and to preliminarily soften it, dissolve and remove a portion of the different constituents dsought to be recovered by this ste the steam supply through pipe 3 is cut o or if the vapors. from the container 13 are utilized, valve or valves19 or 19'@ or both are closed, and the load ot' wood or treated material is removed and introduced into the container wood and that of the exterior causes condensation and an interior movement surfacewise, this action preparing the wood for treatmentI in the next step in the container 13. i

After admission of the wood,l the container 13 is sealed, and valves 16a and 18 are opened, and the vacuum or suction pump 9^ is started to create a vacuum of approximately 15 inches of'water in the container. To quickly attain the vacuum, cold water is forced through spray pipe 38 and onto the wood. The vacuum removes terpenes and like vapors from the Wood, which in passing through coil 8 condenses and 'is discharged into the 'collector-tank 10, for re-use in the process. The vacuum in the container lowers the pressure within the wood below atmospheric causing a cellular expansion which with the removal of the vapors from the wood tends to allow a more ready penetration of the steam employediin the next step in the process. Valve 18 is closed, and valve 14a is opened and live. steam is admitted into vthe container 13, through perforated pipe 14 to create a pressure in the container of about 15 lbs., above atmospheric, and a corresponding temperature of approximately 250 degrees F., `which destroys the vacuum, and raises the temperature and pressure in the wood. This steaming step is prolonged for a period of'QO minutes, more or less. This step vapories a ortion of the oils and some of the remain-l ing ter nes, and repares the soluble ingredients or more e. ective action of: the superheated liquid` employed in one of the succeeding steps inthe process. In addition, steam under pressure, mixed with the vapors of the terpenes following the vacuum will more eectively act u on the interior oit the wood thus accomplis ing results that could not be attained in the sweat chamber.

. ln addition to the steam, heatis maintained by means of the heating coils 15. At .the i conclusion of this step the steam pressure within the container is lowered, valve 18 again opened, and the vacuum pump 9 1s started to create in the container a second.-

vacuum Vof about 20 inches. This sudden change of pressure around the wood causes the pressure within thel wood toorcetheymelted materials in the wood towards the surface and as the second vacuum. .is quickly created, thus lowering the boiling point of the materials in the wood, the temperature of which has previously been raised to 250 F., the high heat and the lowering pressure causes the terpenes and gather subthrough pipe 19.into the sweat chamber, the

justment and allows-of a quicker and more efective penetration into the wood of the.

superehated liquid, which is next introduced in'tp the container from tank 20.

The condensate from collector tank 10, is pumped into thetank 20, and mixes with the water therein, and the condensed terpenes and vapors become mixed with the superheated liquid and add to its solvent power. The valve 23', is opened and the superheated liquid passes from the tank 20, lto the container 13. The movement of the liquid from the tank 20 to the container is` assisted by opening the valve 37, and startlng the air compressor 33, the compresse air acting upon the top of the body of liquid in tank '20. Y

' As the su erheatedliquid, containing terpenes, and t e like, from the wood, is introduced into the container, to prevent excess pressure withiny the container and allow the liquid to flow freely into said container, valve 19d is opened and the vapors pass charged vapors being employed as .previously stated, to assist in sweating the wood.' After the liquid is turned -into the container, and the wood becomes submerged, valve 19rl is closed, and steam is turned into the heating coils 15, to maintain the liquid at a temperature above its normal boiling which creates a pressure inthe conta1nerl oint,

or, in other words, the liquid is maintained in a superheated condition.

It will be understood from the above that the vapors collectin the container in a space that by y liquid, a phenomena occurs which cannot4 above the liquid, and it isv to be emphasized roviding this space above the .well be vei; lained, but which insures, 4as a matter of act, a peculiar and most important 'raeticalresult. That is to say,l the super eated liqud contains volatile.e;rtrac tives of wood which act on the wood being treated to remove similar and` other constituents. This superheated liquid acts to re- `move constituents which cannot, experience proves,l be removed by superheated steam or .water either with or without the space. With the superheated liquor of this' invention, the ebullition thereof creates .a' conf stant irregular motion of theentire volume of liquid in the ncontainer, which with the admixed extractives, dissolves and removes constituents which rise into the space above the liquid. Theoretically, certain of these constituents remain suspended in the space,

while others which are affected by the ebul lition of the liquid, and possibly some ac'- tion or reaction due to the gaseous vapors or the'like insuspension, are caused to be returned and mixed with the liquor, with the effect to materially enrich the same. lVhether or not this theory is correct, is problematical, yet it appears that this is at least a plausible solution, as yactual demonstrations have shown conclusively that the substance after treatment is not discolored, though its physical characteristics have materially changed, which tends to prove that substantially all, if not all, of the vital and commercial constituents have been removed. Experience and use of the process has'also demonstrated that in the final analysis, the use of super heated liquor employed very materially improves the grade of the final product and indeed. produces certain constituents whose identity and character at the present time I am unable to determine. As stated, these d results are attributed largely to the fact that the constituents and extractives removed from the substance are all retained in the liquor, and to the provision of a space above the liquor for the reception of the volatile constituentsLand the creation of an action thereon by the ebullition of theI liquor. After an expenditure of a large amount of money and delay in experimentation with superheated water in a closed container with and without a space at the top, a low grade productonly was produced, the substance being .discolored and its condition demonstrated' that complete removal of the necessary constituents was not effected. As a result of this, I finally evolved the present process, the important step of which was the employment of a superheated liquor charged with the constituents ofl the sub- .stance.

It is desirable lto maintain the temper ature of the liquid at or about 250 F., and-maintain a corresponding pressure of about fifteen pounds above atmospheric.

The wood is subjected to the liquid treatment-for a period of approximately one or two hours, depending 'entirely upon the nature and thickness of the wood and the quantity of materials which it is desired to extract from the Wood. The superheated liquid including constituents of the wood ldissolved in water being-of high temperature and pressure, and containing the additional solvents taken from wood, quickly dissolves and extracts liquid' soluble gums and similar soluble constituents, and also quickly extracts acids, oils and tu`'pentines, and introduces the same to the liquid surrounding the wood and furtherv melts and spreads the maecla insoluble resins and acts upon the same.4 As these acids, oils and turpentines are extracted, they add to the solvent power of the liquid'and extract materials in the wood, which would. otherwise be(l substantially unaffected by the water alone. f

The tim-eof treatment under this step of the process, depends upon the nature f the by-products sought to be recovered, and for that reason the treatment lmay be shortened, so as to leave a portion of the resins in the wood, or it may be prolonged and intensiied for such time and to such a degree as to substantially dissolve and extract the entire resinous content of the wood. To this extent,'it is to be noted, that in so far as the degree of removal is concerned the process is not to be limited to time, temperature and pressure as these factors are also controlled by the character of by-product desired to be recovered; the salient feature, however, being the employment -off superheated liquid containing terpenes or turpentines, acids, oils or other extractives of the Wood.

The superheated liquid permeates throughout the entire structure of the Wood, andthe materials acted 'upon by it" are dislodged from their original position in the o wood, and those which are soluble in the liquid are dissolved and, due to the surrounding pressure and the agitation and ebull'ition of the liquid surrounding the wood, the materialswhich have been removed become intermingled or mixed in the entire body of the liquid. The liquid thus becomes charged withthe by-products, the nature of which is largely dependent u on the character of wood being treated. Itllias been found,however, that in practicing the process, the liquid used in the treatment contains turpentines, pyroligneous acid, tar, pitch, resins,'and the like, residue and pine oil, creosote oil and ligneous matter and the, like. Furthermore, aslong ,as the high heat is maintained, and the fact that the liquid is confined, the substances are so thoroughly intermixed in the liquid, as to make it impossible' to independently distinguishthem.

'While the treatment is in progress, the

liberated gases", also becomein'termingled inl the liquid. It has ,been found that these coni'inedogases, ,charged with turpentines,

acids, oils, etc., penetrate the wood and dissolve certain resinous properties, which are' not of themselves soluble in water andthus materially assist in liberating other constituents-of the wood, which are later separated and recovered as by-products. When the wood under treatmenthas been thusLeffectively acted upon by the' superheated liquid -mixed with contained extractives from the wood, the valves 18 and 191 .are opened, and the -vacuum pump started. This sudden release Aof pressure surroundess.

ing the wood% causes the liquid in the wood to expand and to become converted into steam, thereby forcing both soluble and insoluble materials in the interior of the wood towards its surface and into the liquid. This is a very important step in the proc- This step and the preceding one may be resorted to as many times as deemed advisable, the alternate sudden actions acting to effectively withdraw the constituents from the Wood and into the liquid.

The superheated liquid treatment having been completed the valves 18 and 19d are closed and valve 23 is opened and the` liquid from the container is forced back into the tank 20, for reuse. The liquid is hastened from the container by opening valve 35, to introduce heated air under pressure supplied by the airy compressor 33, upon the surface of the liquid.. When the liquid has been removed from the container, the pressure in the container is suddenly lowered byopening the valve 18, and applying cold Water through spray pipe 38 to condense the steam thus causing the liquid in the Wood to expand and become convertedinto steam, thereby movi the melted resins from the interior -of-t e. wood surfacewise and removing the surface resins, this conversion of liquid in the wood into steam be- ,ing due to the fact that previously the liquid in the Wood has' been raised to a temperature .of approximately 250 F. and al corresponding pressure, and the sudden release of pressure to atmospheric reduces the boiling point of the liquid in the' wood,l also alowlng a cellular or brous expansion of Wood Structure progressively from the exterior portions inwardly, which forces the resinous matter surfacewise.' Following this stepa pressure may be again applied within the container by the admission of steam, or heated air or a mixture of both such Apres sure acting on the wood to further expel any contained matters when the desired pressure is attained it is held for a limited time. and is then rapidly reduced, valve 18 -is opened, and the vacuum pump 9 is started, and a vacuum is again created in the 'container 13, .and simultaneously cold Water is sprayed'on the wood through the spraypipes 38, to uickly reduce the pressure and condense t e vapors.` This ste of alterations of pressure' may b e repeate as desired. In this step in the application of the vacuum, the spray of cold water'is preferably employed only in. the initiation of the vacuum, and the vacuum is held for one,y half hour a proximately, depending on the character o thenvood and the substances to be extracted. -At the end of the step, the

vacuum pump is stopped and the escaping moisture from the Woodwill in a few minutes destroy the vacuum, lor if uicker action be desired, 'the valve 14 may e opened,

to introduce steam to the container; The wood or material remaining in the container may now be removed, and a second charge being preliminarily treated in the sweat chamber, is now moved into the container.

In the next and succeeding operations in the container, the liquid is reused until it becomes concentrated to the desired degree, the charged water is drawn off andthe various elements are' distilled, 0r otherwise separated and recovered by mechanical separation, as by the centrifugal separator, or chemical reagents may be employed, or special solvents may be used.

The superheated' liquid treatment may be repeated and alternated with a vacuum, t0

insure of the extraction of the elements from the wood, as it has been found that the wood structure when first opened up by the action of the water and then acted on by a vacuum, will give off further some of .the constituent elements.

The superheated liquid step having been finished, and if it be desired to recover the resins and the like, a vacuum is again produced by starting the pump 9, to prepare the wood for the next step. The .vacuum pump is stopped, and the valves 55 and 52 are opened and the superheated chemical solution in the tank is violently introduced into the container 13, which breaks the `vacuum in the latter, steam and heat in pipes 14 and 15 maintain the high tempera ture and ressure in the container, being maintaine by steamin the pi s 14 and 15. The superheated chemical so ution acts to dissolve and remove the ligneous and resinous substances from the wood to the water in solution, which are afterwards recovered by any well known process. Aftery a short treatment of the wood 'with the chemical solution, valve l is closed,.valves 52 and 35 are opened,`and pressure from the pump 33 returns the -solution from the container 13 to the tank 50, for further use.

Some of the solution and perhaps some of the ligneous and resinous substances still remain in the wood, and to recover both, I employ cold water to wash them out. Valves 52 and 35 are closed and valve 62 is opened and pressure from pipe 63 forces cold water from the-reservoir into con- .tainer 13.

rlhe difference between the high temperature of the wood and the low temperature of the water causes the moisture containbe afterwards recovered.

This step in the treatment is completed, and then the water is forced back into the reservoir for reuse.

The chemical solution and the cold water become mixed with the resinous substances from the wood, and therefore become agents Vherein employed, I intend to define a liquid or liquor at a temperature above the normal boiling point of such, this temperature to the degree contemplated being permitted b v maintaining the liquid or liquor at such pressure as will permitl the use of the desired temperature without inducing a free boiling action of the liquid or liquor.

The -process is in no way limited to use in connection with wood, as it is evident all plant substances may be acted upon to recover the various by-p'roducts.

From the foregoing description, it will be seen that I so treat the wood as to trap and recover the by-products from the wood when either extracted in the form of vapor, or when dissolved and dislodged in and by superheated liquid. Every element given off in the treatment is recovered and is, of

water, the said.l water bein further enriched and charged with volati e extractives removed or liberated from the substance during the progress of the treatment, to thereby remove constituent materialfrom the substance being treated, removing the charged water, and thereafter separating the contained extractives from such charged water.

2. The process of removing' volatile and other extractives from'a resinous solid plant substance,Y consistin in first subjecting the plant substance to ot vapor charged with the volatile constituents from a resinous wood to vheat the substance and preliminarily soften and impregnate the substance with the extractives contained inthe vapor, then while'the plant substance is still hot subjecting it to water at a temperature above its normal boiling point, with said water charged with all volatile extractives from a resinous wood resulting. from a previous treatment of such wood with superheated water, the said water beino 'further enriched and charged with volati e extractives removed or liberated from the substance during the) progress of the treatment, to thereby remove constituent material from the substance being treated, removing the mereca charged water, and thereafter separatingthe conta-ined extractives from such charged .resinous wood resulting from a previous treatment of such wood with superheated Water, the said Water being further enriched izingall of the condensate for charging s uperheated Water to dissolve and remove the Water-soluble constituents of the substance and melt a portion of the Water-insoluble constituents of the substance, collecting the vapors charged with the constituent materials resulting from the treatment and conand charged with volatile extractives re` moved or liberated from the substance during the progress of the treatment, to thereby remove constituent material from the substance being treated, the treatment being carried out while the substance is free from contact with the air, removing the charged water, and thereafter separating the contained extractives from such charged water.V

' 4. The process of extracting constituent materials of a resinous solid plant substance', consisting in submerging the plant substance in superheated waterwhich has been previously employed in treating a resinous solid plant substance Iin a manner .to incorporate in the waterconstitutent materials of such substance, trapping and condensing the vapors rising from the superheated water and Vsubsequently introducing such condensate into the superheated water for enriching the same, withdrawing the charged superheated water with the contained constituent materials of the substance, subjecting the plant substance to a vacuum lto 'furtherremove moisture and constituent materials .in .a more or less vaporous form, and condensing the vapor.

5. The process. of extracting constituent materials of a resinous solid plant substance, consisting in subjecting the plant substance to moist hot ainand vapor to recover` the constituent materials, suddenly reducing the pressure on'the surface of the material being treated to thereby cause a. movement, of the moisture andl materials contained in said densing such vapors, and thereafter drawing off the water containing the remaining constituent materials for future separation.

7. The process of extractingconstituent materials of a resinous solid plant substance, consisting in subjecting the substance to moist liOt atmosphere, suddenly reducing the surface pressure on the substance to cause the interior moisture to mo've toward the surface of the substance and carry withit .constituent materials, collecting and conplant consisting in collecting an densing the vapors for separationA of the constituent materials, subsequently submerging the plant substance in ,superheated water charged vith the condensate, collecting the vapors rising from the superheated water and charged with the constituent materials for future separation of such materials, and thereafter withdrawing the water to permit the recovery of the contained constituent materials.

8. The procese of extracting constituent materials of a resinous solidplant substance, removing the vapors from the substance while in a hot state, and then suddenly reducing the surface pressure on the substance byspraying the substance with cold waterin a closed space to cause the contained constituent materials to movefsurfacewise while the sur- .face of the substance is maintained at subtemperature sufficient to melt the resins in substance toward the 'surface thereof, then f submerging the substance in superheated .water to destroy the vacuum therein and dissolve and remove water-soluble constituents and melt a portion of the water-insoluble `constituents and cause the same to intermingle with the superheated water, condens ling the vapors rising from the water, then removing the Water and reducing the ressure on the substance below atmosp eric pressure to withdrawl further vapors,and

the substance, and subsequently subjecting the substance to the action of a vacuum and heat to remove a portion of the moisture charged with the constituent materials of the substance, and thereafter recovering .such materials.

finally condensing the vapors to recover the contained portion of constituent materials.

6. The process of extracting constituent materials of\a resinous solid plant substance, 'consisting in treating a load ofthe substance to hot moist atmos here to sweat it, tra/.p-l

ping the vapor `an condensing same, yutil- 10. The rocess of extracting constituent materials o 'a resinous solid plantsubstance, consisting in raising the interior pressureof the substance above that of the atmosphere by contact with steam under pressure, then suddenly loweringthewsurface pressure of the substance by condensing the steam surrounding the substance vby spraying with cold water.

11. The process of extracting constituent materials of a resinous solid plant substance,

consisting in subjecting the substance to hot water charged with constituent materials of such substance in a liquid state at a pressure above atmospheric, then suddenly reducing the surface pressure of the substance to atmospheric pressure to cause the constituent materials and water within the substance to move surfacewise and from the substance into the surrounding water, andV recovering the constituent materials.

12. The process vof extracting constituent materials of a resinous solid plant substance, consisting in subjecting the substance to hot water charged with constituent materials of such substance in a liquid state at a pressure above that of the atmosphere, then suddenly reducing the surface pressure surrounding the substance to a pressure materially below that of the first mentioned pressure to cause the contained constituent materials and water within thesubstance -to move toward the surface ofthe substance and into the surrounding water.

13. The process of extracting constituent materials of a resinous Lsolid plant substance, consisting in submerging the substance in hot water previously charged with constituent materials of the substance in a liquid state to act on the Water-soluble constituent materials of such substance, then expelling a portion of the water and contained constituents Within the substance into the surrounding water by creating relative pressures around and within the substance; then removing the water While simultaneously applying air under pressure above the Water suiiicient to maintain -the residual constituent materials within the substance under pressure,A then suddenly lreducing the air pressure to cause the residual constitutent materials within the substance to expand and travel to and beyond the surface-of the substance. i

In testimony whereof I -aiix my signature.

` FREDERICK K. FISH, JR. 

